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Title: Elemental and Molecular Segregation in Oil Paintings due to Lead Soap Degradation

Journal Article · · Scientific Reports
 [1];  [2];  [3];  [4];  [4];  [5];  [6]; ORCiD logo [4];  [3]
  1. Stony Brook Univ., NY (United States). Department of Materials Science and Chemical Engineering; Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  2. Montclair State University, Montclair, NJ (United States). Department of Chemistry and Biochemistry
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
  4. Univ. of Delaware, Newark, DE (United States). Department of Chemistry and Biochemistry
  5. Independent Researcher, Rochester, New York, NY (United States)
  6. The Metropolitan Museum of Art, New York, NY (United States). Department of Scientific Research
+ Show Author Affiliations

The formation of Pb, Zn, and Cu carboxylates (soaps) has caused visible deterioration in hundreds of oil paintings dating from the 15th century to the present. Through transport phenomena not yet understood, free fatty acids in the oil binding medium migrate through the paint and react with pigments containing heavy metals to form soaps. To investigate the complex correlation among the elemental segregation, types of chemical compounds formed, and possible mechanisms of the reactions, a paint sample cross-section from a 15th century oil painting was examined by synchrotron X-ray techniques. X-ray fluorescence (XRF) microscopy, quantified with elemental correlation density distribution, showed Pb and Sn segregation in the soap-affected areas. X-ray absorption near edge structure (XANES) around the Pb-L3 absorption edge showed that Pb pigments and Pb soaps can be distinguished while micro-XANES gave further information on the chemical heterogeneity in the paint film. The advantages and limitations of these synchrotron-based techniques are discussed and compared to those of methods routinely used to analyze paint samples. The results presented set the stage for improving the information extracted from samples removed from works of art and for correlating observations in model paint samples to those in the naturally aged samples, to shed light onto the mechanism of soap formation.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1413937
Report Number(s):
BNL--114538-2017-JA
Journal Information:
Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 7; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Evaluation of the “added value” of SIMS: A mass spectrometric and spectroscopic study of an unusual Naples yellow oil paint reconstruction journal July 2009
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SEM Backscattered-Electron Images of Paint Cross Sections as Information Source for the Presence of the Lead White Pigment and Lead-Related Degradation and Migration Phenomena in Oil Paintings journal April 2011
Pigment Degradation in Oil Paint Induced by Indoor Climate: Comparison of Visual and Computational Backscattered Electron Images journal February 2016
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The crystallization of metal soaps and fatty acids in oil paint model systems journal January 2016
Protrusions in a painting by Max Beckmann examined with confocal μ-XRF journal January 2011
Early science commissioning results of the sub-micron resolution X-ray spectroscopy beamline (SRX) in the field of materials science and engineering
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Metal Stearate Distributions in Modern Artists' Oil Paints: Surface and Cross-Sectional Investigation of Reference Paint Films Using Conventional and Synchrotron Infrared Microspectroscopy journal October 2012
Nuclear Magnetic Resonance Spectra and 207 Pb Chemical-Shift Tensors of Lead Carboxylates Relevant to Soap Formation in Oil Paintings journal March 2014
Analysis of Lead Carboxylates and Lead-Containing Pigments in Oil Paintings by Solid- State Nuclear Magnetic Resonance journal July 2014

Cited By (5)

Revealing the Distribution of Metal Carboxylates in Oil Paint from the Micro‐ to Nanoscale journal July 2019
Revealing the Distribution of Metal Carboxylates in Oil Paint from the Micro‐ to Nanoscale journal July 2019
Unravelling the spatial dependency of the complex solid-state chemistry of Pb in a paint micro-sample from Rembrandt's Homer using XRD-CT journal January 2019
2018 atomic spectrometry update – a review of advances in X-ray fluorescence spectrometry and its special applications journal January 2018
Time-Resolved Photoluminescence Microscopy for the Analysis of Semiconductor-Based Paint Layers journal November 2017

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